Warm water-dilutable paste rosin size and process for the manufacture thereof



March 18, 1969 M. J. D'ERRICO ETAL 3,433,353

WARM WATER-DILUTABLE PASTE ROSIN SIZE AND PROCESS FOR THE MANUFACTURETHEREOF File'd Jan. 17. 1968 II n 70m/0W anvar/1175* INYENTORS. MICHAELJ. D ERR/C0 RUSSELL J. KUL/CK ATTORNEY United States Patent O 3,433,658WARM WATER-DILUTABLE PASTE ROSIN SIZE AND PROCESS FOR THE MANUFACTURETHEREOF Michael Joseph DErrico, Stamford, Conn., and Russell JosephKulick, Lee, Mass., assignors t American Cyanamid Company, Stamford,Conn., a corporation of Maine Continuation-impart of applications Ser.No. 413,603, Nov. 24, 1964, and Ser. No. 584,194, Oct. 4, 1966. Thisapplication Jan. 17, 1968, Ser. No. 698,655 U.S. Cl. 106-123 8 ClaimsInt. Cl. D21c 3/00; C11d 15/04; C09f 1/04 ABSTRACT OF THE DISCLOSURE Afluid rosin size consisting of an aqueous dispersion of a rosin saponiedat least 85% with an alkali metal of which at least about 75 =molpercent of the metal cations are potassium, and 9-20% of an anti-gelagent selected from the group consisting of ethanol and iso-propanol,the rosin size solids content of said size being between about 65% and80% by weight.

This is a continuation-in-part of our copending applications Ser. Nos.413,603 and 584,194, respectively tiled on Nov. 24, 1964 and Oct. 4,1966 and now abandoned.

The present invention relates to paste rosin size of improved uidity andof improved dilutability with water to a solids content of less than 10%by weight. More particularly, the present invention relates to pasterosin size which is of pumpable viscosity at normal storage temperatureand which in preferred instances is of pumpable viscosity at roomtemperature', and which can be readily diluted with warm and inpreferred instances with cold water to a solids content of less than 10%by weight,

and to processes for manufacturing and 4diluting such size.

Rosin size is customarily manufactured by partially neutralizing apapermakers rosin (gum rosin, tall oil rosin, fumarated rosin,formaldehyde-reacted rosin, etc.) with aqueous sodium hydroxidesolution. The amount of sodium hydroxide is predetermined so that therosin is neutralized or saponitied to the extent of about 75 85% and theamount of water is predetermined so that the resulting size is barely ofpumpable viscosity at normal storage temperature (170 F. or 71 C.) toavoid the necessity of shipping more water than is absolutely necessary.The resulting rosin is termed paste rosin size, and contains about65%-80% rosin size solids by weight. Check U.S. Patent No. 3,321,325. Itis a sticky almost solid mass at room temperature, but becomes a viscouspumpable fluid when hot. It is consequently prepared for shipment at ashigh a temperature as is practical (in the range of 150 F.210 F.) and isshipped suiiiciently rapidly so that it is of pumpable viscosity whenreceived by the user.

Paste rosin size is generally transported by tank cars and is dischargedfrom the cars by pumping. The cars are thermally insulated but receiveno heat. They consequently cool in transit more or less, depending onthe length of the trip and the season of the year. If the size arrivesat a non-pumpable viscosity when received by the user, it must bere-heated, and this is a slow and inconvenient task, which, if notperformed carefully, may burn the size.

Moreover, the size must be diluted to low (2%-5%) solids content beforeit can be used in papermaking. Dilution of paste rosin size with coldwater presents a serious diiculty, which arises as follows.

3,433,658 Patented Mar. 18, 1969 When a quantity of hot paste rosin sizeis mixed with a quantity of cold water, the size transforms itself intoa stiff gel, after which further dilution of the size -becomes ydilicultand slow. This phenomenon is generally regarded as independent of theextent to which the rosin has been saponied and occurs even in the caseof a rosin size wherein the rosin is completely saponiiied, so that therosin size contains no free rosin acids at all. 'Ihe phenomenon isdescribed more in detail in Howell U.S. Patent No. 2,573,024 (1951),which discloses a number of expedients for overcoming this difficulty.

The discovery has now been made that rosin size which consistsessentially of an aqueous dispersion of a rosin which is at least 85%saponiiied with an alkali metal alkali at least about mol percent of themetal cations of which are potassium, and which contains between about2% and 20% (based on the weight of rosin size solids in the size) of awater-soluble saturated monool, is fluid (i.e., is of pumpableviscosity) at standard storage temperatures when of rosin size solidscontent between 65% and 85% by weight, yet is readily dilutable withwarm (40 C.) water and inA preferred instances with cold and even withice water through the range of solids at which formation of a stiffslow-dissolving gel would otherwise occur. In other words, We haveydiscovered that paste rosin size of the composition described does notpass through a viscous gel stage when it is extensively diluted withWater in any amount.

The size of the present invention possesses the following advantageousproperties:

(1) It can be diluted to as low as 1%5% solids by introducing the size,at a temperature at which it is uid, into an appropriate amount of warmwater or in preferred instances cold water with gentle agitation (c g.,sufficient agitation to break up the size into small globules). Theglobules 4dissolve within a few minutes; the result is a clear soapsolution. As a result, an excellent size solution is easily and quicklyobtained at high dilution direct from paste rosin size without need forspecial equipment.

(2) The invention permits a major economy in the handling of rosin size.Heretofore, tank cars of rosin size have typically required 36 hours tobe discharged at 160 F. The size of the present invention, because ofits greater fluidity, can be discharged under similar conditions in 6hours. Moreover, in preferred instances, sizes of the present inventionat solids content of 70% or more are of pumpable viscosity attemperatures down to 60 F. Hence tank cars containing such size canusually be discharged at the .temperatures at which they are received bythe customer, and need not be reheated.

(3) The size of the present invention is used in the manufacture ofpaper in the same manner as ordinary rosin size, and the papermanufacturer need not learn any new techniques. Paper having a contentof the size of the present invention is of normal appearance andproperties.

The invention is further illustrated by the drawing, which is athree-dimensional graph showing the principal parameters of rosin sizein general (parameters A, B, and C), of the size of the presentinvention viewed generically (parameters D, E, and F), and of onepreferred embodiment of rosin size of the present invention (parameter-sG, H, and I).

In the drawing, parameter A represents the mol percent of potassium ionswhich may be present in rosin size (based on the total number of mols ofmetal ions present); parameter B represents the weight of saturatedmonool which may be present based on the weight of rosin size solids inthe size, and parameter B represents the extent (mol percent) to whichthe rosin in the size has been saponiiied.

Parameters D, E, F define the rosin size of the present inventiongenerically. As shown by parameter D, at least about 75 mol percent ofthe metal ions in the size are potassium ions. As shown by parameter E,the size contains between about 2% and 20% of a saturated monool basedon the weight of the size solids in the size. As shown by parameter F,the rosins in the size are at least about 85% saponied. The sizes thusdefined are of pumpable viscosity at normal storage temperatures andrapidly and completely dissolve to 1% solids when gently stirred inwater at 40 C.

In one preferred size illustrated, at least S5 mol percent of the metalions are potassium ions as is shown by parameter G, the amount of themonool is 9% to 12% of the weight of rosin size solids in the size as isshown by parameter H, and the amount of the rosin which is saponied isat least 85%. This size at rosin size solids content of 60%-75% is fluidat room temperature and dissolves to 1% solids readily even in water atroom temperature. It may but need not contain a larger proportion ofmonool.

In another instance, the size is of about 80% rosin solids size content,the rosin therein is 85%-90% saponied. The weight of the monool is 2%-4%of the weight of rosin size solids in the size, and more than 95 molpercent of the metal ions in the size are potassium ions. Such size,although containing a very small amount of monool, dissolves readily to1% solids in warm (50 C.) water.

When the rosin is more than 95% neutralized, when more than 95 molpercent of the metal ions are potassium, and when the amount 0f monoolis 9%-20% of the weight of size solids, the size is of pumpableviscosity at room temperature and is readily soluble in ice water.

When the proportion of potassium cations to all the metal cationspresent in any given size of the present inven tion is decreased belowabout 75%, the size becomes unduly ditlicult to disperse even in warmwater, and hence the resulting size is outside the present invention.

When the amount of saturated monool and the extent of saponication ofthe rosin are below the indicated minimum in any instance, the sizetends to form a stili gel on admixture with water, and such size too isoutside the present invention. Excess monool (i.e., more than based onthe weight of size solids) is disadvantageous because the excess monoolincreases the unit cost of the size without contributing any significantoff-setting advantage. On the other hand the rosin may advantageously besubstantially completely saponilied, and substantially cornpletesaponification is preferred where lowest fluidity and maximum ease ofdispersibility in water are desired.

The term cation as used in the present application designates not merelymetal ions in dissociated state, but also metal in combined rosinateform as, for example, in potassium rosinate. Preferably, substantiallyall the cations of the size of the present invention are potassium as insuch instance the size possesses better dispersibility than wouldotherwise be the case.

The saturated monools which are present in the 4size of the presentinvention include the water-soluble C1-C4 alkanols, for instancemethanol, ethanol, propanol, isopropanol, butanol, t-butanol, andisobutanol, and saturated lower monohydric alcohols such as3-chloro-lpropanol, 2-methyloxyethanol, ethanolamine, and2-nitroethanol. Mixtures of these or other similar lower monools may beused. So far, isopropyl alcohol has proved the most effective monool ona cost basis and posesses nearly the effectiveness of ethanol withoutpossessing its great volatility and is therefore preferred. Humectantdiols (for example, ethylene glycol and glycerol) predispose the rosinsizes of the present invention to gel when diluted with water, andtherefore should not be used.

The monool content of the size is at least that amount which preventsformation of a viscous gel when the size is diluted with water. For thispurpose, 2% of the monool is about the least amount which is effective.Size containing this amount of monool is of pumpable viscosity and thegel which it forms when it is mixed with water dissolves rapidly. On theother hand it is generally unnecessary for the amount of monool to bemore than about 12% of the weight of the rosin size solids, and thelatter amount is therefore regarded as satisfactory to most commercialusers.

We have found that sizes containing 9%-12% of the monool andsubstantially no free rosin acid are especially beneficial when the onlymetal cation present is potassium. In such event, the size possesses themost important and surprising properties of being a mobile liquid atroom temperature and at solids, and of dispersing rapidly in ice waterwith no more than moderate agitation. The amount of monool mayadvantageously be larger, up to about 20%, and such larger amount isspecially advantageous when the size is to be pumped long distances incold weather.

The paste rosin size of the present invention can be manufactured bysaponifying any of the numerous papermakers rosins (such as have beennamed above) with an alkali at least of the cations of which arepotassium, and adding a saturated monool, the amounts of water, monooland alkali, and the proportion of potassium cations to the other metalions therein, being predetermined so that the size falls within theparameters D, E, and F of the drawing and is of pumpable viscosity at F.while having a rosin size solids content of at least 60% by weight.

Suitable proportions are readily established in any instance bypreparing a series of sizes in the laboratory, and determining theviscosity of the size and the amount and solubility of the gel which itforms during dilution with water. Formation of insoluble orslow-dissolving gel or too high a viscosity indicates that thecomposition should be modified in the direction of parameters G, H andI.

In rosin size manufacture, the term pumpable viscosity is generallytaken to mean a viscosity of about 3,500 centipoises (Hoeppler), but inspecial instances a size of higher viscosity is regarded as pumpable,depending on the power of the pump which is available, the length ofpipe through which the size must be pumped, the number of bends in thepipe, etc.

The saturated monools generally do not react with the alkali or with therosin or rosin size. Consequently they can be introduced during or aftersaponication. However, they are volatile at the temperatures at whichrosin is saponied, and hence in instances where the saponication step isperformed in an open vessel, they are most conveniently metered into thesize as it is pumped into closed storage tanks or into tank cars forshipment.

When the size is made in a continuous saponier such as is shown inAnderson et al. U.S. Patent No. 2,842,453 the alkanol may be introducedas a component of the caustic solution or into the discharge from thesaponier as preferred.

Dilution of the r-osin size of the present invention is readily affectedin one step from 60%-80% rosin size solids by weights to 2%-5% rosinsize solids by agitating the size with an appropriate quantity of water.The temperature of the water should be that at which the size undergoesrapid and complete dispersion. Homogenization or even intensiveagitation is not required. lf preferred, a continuous stream of dilutesize can be provided by introducing the size as a iine stream into waterin turbulent ow. The minimum suitable temperature of the water in anyinstance can be determined by introducing the size through a hypodermicneedle into a beaker of water agitated by a propeller-type stirreroperating at moderate speed. Formation of globules of size whichdissolve rapidly and completely show that the water is of suitabletemperature. Slow or partial dissolution of the size shows that thetemperature of the Water should be raised.

The monool does not appear in the paper when the size is employed inpapermaking, but remains in the white water. The monool thus has nosignificant effect upon the amount of water resistance, lactic acidresistance, etc., which is imparted by the size.

The paste rosin size of the present invention may contain minor amountsof other materials such as are customarily present in paste rosin size,for example, sodium side Wall lof the beaker to act as bae. Sizes areregarded as dispersible when a clear solution or dispersion forms withinthree minutes. The presence of iloc or other insoluble matter in thewater at the end of three minutes is evidence of only partialdissolution of the size and indicates that the size is unsatisfactory.

The tests show that the sizes can be satifactorily dispersed in waterwithout homogenization.

Description of Sizes l Autodilutaability i in H2O Appearance PercentPercent Percent Saturated Monool at of Solutions Run No. Rosin SolidsRosin 3 Saponied 2 Percent 4 Name 20 C. 50 C.

Tall oil 5 75 90 None N G. N. G. (9). G 75 90 100 N. G. N. G. (D) 75 90100 1 N.G. N.G. (9). 75 90 100 2 N. G. O.K. Clear. 75 90 100 3 N. G.O.K. Do. 75 90 100 3 N.G. O.K. D0. 75 90 100 2 N.G. O.K. Do. 75 90 75 2N.G. O K. Do. 75 95 100 4 O.K. O.K. Do. 75 85 100 2 N. G. O.K. D0. 75 90100 2 N.G. O.K. Do. 75 85 100 4 O.K. O.K. Do. 75 100 100 5 O.K. O.K. Do.75 90 100 3 N.G. O.K. Do. 75 95 100 4 O.K. O.K. Do.

1 Based on the weight of the size.

2 Molpercent of rosin acids saponified.

3 Metal cation content (mol percent) of size.

1 Based on Weight of solids in lsize.

5 For description of test, see text above.

5 Tall Ioil rosin somerized ait 275 C. for 30 minutes.

or potassium acetate, chloride or nitrate, as fluidifying assistants;pentachlorophenol as mold growth inhibitor, a cationic resin or limoneneas auxiliary fortier; and emulsified wax or a hydrophobic syntheticthermoplastic resin as a supplementary size.

The invention will be further illustrated by the examples that follow.These examples are illustrations of the invention and are not to beconstrued as limitations thereon.

Example 1 The following illustrates a number of rosin sizes according tothe present invention which are fluid at 170 F and which dissolvecompletely 1% solids without homogenization rapidly in warm or coldwater in one step, without formation of slow-dissolving gel.

The sizes are prepared by saponifying a rosin with aqueous potassiumhydroxide (or with an aqueous mixture of potassium hydroxide and sodiumhydroxide); the amounts of alkali and water are pre-determined so thatthe free acid content and size solids content in the resulting size isas shown in the table below, which also shows the particular rosin whichis saponified in each instance and the m-ol percent of potassium ions inthe size. There is then stirred into the sizes at 70 C. a C2 0r C3saturated monool, as is shown in the table below.

Control sizes are prepared without use of potassium alkali or anysaturated monool, and a control size is prepared by luse of a potassiumalkali but with an insufficient amount of monool.

The control sizes do not dissolve in water at 50 C.

The remaining sizes which exemplify sizes of the present inventiondissolve readily when parts (or less than l0 parts) by weight of thesizes are stirred into 90 parts of water at 50 C. In several instances(where the rosin is more than 90% saponied and the amount of alkanolpresent is 8-12% of the weight Iof size solids), the sizes dissolvereadily when the temperature of the water is C. or less.

The dispersibility test is performed by dropping 1.0 g. of size at 65 C.from a hypodermic syringe into 99 g. of water having the temperatureshown in the table contained in a Z50-cc. laboratory beaker rotatingfrom the effect of a magnetic capsule turning at 1500 r.p.m. and thenplacing a 1/2" wide spatula vertically along the in- Taillall oil rosinreacted with 1/5 m01 of fumarie acid at 8 Tall oil rosin reacted `with1/5 mol of paraforrnaldehyde at 150 C. and heated for 30 minutes at 275C.

9 Size Adoes not dissolve. When stirring fstops, size droplets settle tobottom of beaker and form a layer.

The rst three (control) runs show that when the amount of monool is toolow, the resulting size is not dispersible in warm water even when allof the metal ions present are potassium.

Example 2 The following illustrates a fluid rosin size according to thepresent invention which is cold water dilutable to 2% solids in one stepwithout homogenization to form a clear solution.

A mixture of (a) 178.0 g. of tall oil rosin fortified by a reactedcontent of fumaric acid and (b) 460.2 g. of tall oil rosin having areacted content of 9.0 g. of paraformaldehyde and which had subsequentlybeen heated at 275 C. for 15 minutes to decrease its latent foamingcapability is melted in a vessel provided with stirrer and refluxcolumn. To the mixture is slowly added a mixture of g. of water at C.having a dissolved content 9.0 g. of sodium chloride, and 221 g. of a45% by weight aqueous solution of potassium hydroxide. The mixture isheated to reux. After about 15 minutes, when saponication is complete,the mixture is cooled to 70 C., 17.9 g. (3% based on the weight ofsizing solids) of isopropyl alcohol is added, and the mixture is allowedto cool. The product contains about 80% solids by weight and 13% freerosin acid (equivalent to about 87% saponication), and has a viscosityof 1500 cp. at 170 F. The size dissolves rapidly and completely when 2g. is introduced as droplets from a hypodermic syringe into 98 g. ofwater at 50 C. which is gently stirred in a laboratory beaker. A clearsolution forms.

Example 3 The following illustrates a fumarie acid-fortifiedformaldehyde-containing rosin size according to the present inventionand further shows a preferred method of diluting the size in one stepwith water.

To 302 g. (l mol) of tall oil rosin is added with stirring at C., 6.0 g.(Ms mol) of paraformaldehyde. After ve minutes the mixture is heated to275 C. and is maintained there for 30 minutes. The mixture is cooled to200 C. and 23.2 g. (1/5 mol) of fumaric acid is added with stirring.After two hours at that temperature the resulting resin is cooled to 140C. and saponified in an 7 8 open vessel by adding thereto a solution of70 g. of potas- Six aliquots each weighing 89.8 g. (and containing 67.6sium hydroxide in 130 g. of water. A fluid rosin size of g. of sizesolids) are removed. To each is added with 75% solids and 8% free rosinacid content is obtained. stirring 6.8 g. of one of the monools shownbelow. The

There is then added with stirring 15.0 g. (4% on the samples eachcontain 10% of monool based ori the dry weight of sizing solids) ofisopropyl alcohol. The Viscosity weight of the solids therein; theproducts are paste rosin of the product is such that it is a fluidviscosity at C. 5 size containing 70% solids by weight. The samples areThe size dissolves rapidly when aspirated through a placed in 100 cc.vials kwhich are capped and cooled to pipe 1A6" in diameter into waterat 20 C. flowing at a 25 C.

brisk pace from a laboratory faucet through a pipe about The presence orabsence of gel in the samples of size 1A in inside diameter. Thedischarge from the pipe is a 10 is determined in each instance byobserving the flow made clear solution and contains about 7% by weightof rosin of the size when a cylindrical vial is quarter-filled with sizesolids. a sample of the size at 18 C. and the vial is u1u-ended, so thatthe size flows over the inside of the vial as a Example 4 thin film. Asize which ows freely, as a clear amber The following illustrates thepreparation of a preferred 15 uld Wlihout trlatlons (bke map1e Sym?) ,1Sfree frm size of the present invention and the outstanding solugel' Aslze which ow ffeeiy 'but mib s matlons miams bility properties which itpossessesgel, but of the type `which dissolves within a commercially To100 g of tau oil rosin at 200 C is added 16 g of acceptable time. A sizewhich flows rapidly in a stringy fumarie acid with stirring, and themixture is maintained Pattern contams .a cfmmerclauy unafceptafbly largeat 200 C. for 2 hours' To the product is added 300 g- 20 amount of -gelwhich is of the type which dissolves in of tall oil rosin which hadpreviously been reacted with too lorlg a time* Slow ow 1S eYldence ofthe presence of 2% by weight of paraformaldehyde at 160 C. and then Slow.dlsolvmg gel arid Such Size may appear to be free heated at 275 C for30 minutes. of Strlatlons and strmginess The resulting mixture is cooledto 125 C. and is sub- .The Compara/uve vlscoslty of. the. size 1S thendeter' stantially 100% saponied by addition of 78.4 g. of potas- 25 useof a Brookeld vlscoslmeter at 100 r'p'm sium hydroxide in water. an

To the resulting size is added 115 g of potassium The comparative easewith which the sizes can be chloride 48 g of isopropyl alcohol (10% onthe Weight diluted with cold `water is determined by gently stirring ofsize solids) and suicient water to adjust the solids With a Spatula 2-5g- Of the SiZ iI 1 each instance iIlO content 0f the size to 70% 30 97.5g. of water at 18 C. and recording the time required The resulting sizehas a viscosity of less than 200 foraclear and sparkling solution toform. centipoises at 71 C. and is of pumpable Viscosity (ap- Results areas follows.

Monool Visc. of size l Percent Flow mode ofsize2 Amount Cp. at PercentDilute- Naine added of gel C. decr. bility of size Run No..

1 Methanol 10 46.8 6 2 Ethanol 10 77. 8 5 3..- n-Propanol 10 71. 4 5 4-Iso-propanol. 10 72.5 3 5 n-Butanol 10 60.5 11

1 Based on solids in the size.

2 Observed by reversing vials of size at 18 C. Fast=like maple syrup.

3 See text above. Much indicates gel is of putty-like consistency;slight indicates that size is easily fluid and that only faintstriations are observable during flow.

Minutes to form clear 2.5% by weight solution, when pipetted with gentlestirring into water at 18 C.

proximately 3500 centipoises) at 15.5 C.,'and dissolves We claim:rapidly when stirred into ice water. 1. Fluid rosin size of betweenabout 65% and 85% The size prepared above imparts substantially the Samesolids content which is of pumpable viscosity at standardwater-resistance to paper as the size described in Exstora-getemperatures and which uniformly dissolves to a amples 1-3. clearsolution when one part by weight is stirred with 99 The size of Example4 illustrates our discovery that parts by weight of water at 40 C.,consisting essentially size of extraordinary fluidity and dispersibilityin cold of an aqueous dispersion of a rosin at least about 85 water isachieved when the size contains substantially no saponified with analkali metal alkali at least about 75 free rosin acid, whensubstantially all of the metal cations mol percent of the metal cationswhich are potassium, in the size are potassium, and when the amount ofand as an anti-gel agent, between about 9% and 20% riionool in the sizeis between about 8% and 12% of the (based on the weight of rosin sizesolids in said size) of weight of size solids in the size. At 71 C.these sizes are a C1-C4 saturated monool, the rosin size solids contentfluid liquids even lwhen their size solids content is as of said sizebeing between about 65% and 80% by Weight much as by weight. and theweight of water in said size being greater than the weight of saidmonool.

2. Rosin size according to claim 1 which when of 60%- rosin size solidscontent disperses readily in water at 20 C. wherein the rosin is morethan 85% neutralized, the weight of the nionool is 9%-12% of the weightof ing 600 g. (2.3 mols or equivalents) of commercial fortirosin sizeSolids i? th? Sife more thai? m01 percent ed rosin (tau oil rosin foredby a content of 2/10 m01 of the metal ions .in said size are potassiumions, and the of fumarie acid), adding 246.5 g. of a 45.6% by weight 70temperature of Sald S12/e 1S below 100 F- ZExample 5 The followingillustrates the comparative effectiveness of a number of Cl-Ci monoolsin paste rosin sizes of 65 the present invention.

A master batch of paste rosin size is prepared by heatsolution ofpotassium hydroxide in water 2.0 mols) and 3' Rosin Size according i0Claim 2 wherein the TOSiIl g of Water stirring, and maintaining thereaciS more than neutralized and 'wherein more than tion mixture at 90C. with stirring. The water lost by m01 Percent 0f the metal iOTiS arePotassium, Said Sile evaporation is then replaced; the product is pastesize being of pumpable viscosity at room temperature and weighing 898.4g. of which 676.4 g. (75.3% is solids. 75 being readily soluble to 1%solids in ice water.

4. Size according to claim 1 wherein the rosin is a References Citedfumarafed rOSirl- UNITED STATES PATENTS 5. Size according to claim 1wherein the rosin is more 2 262 454 11/1941 F1 enner 106 237 than 95%Saponied- 2,373,203 2/1959 Hopkins et a1 E 10s- 233 6. Size according toclaim 1 `wherein substantially all 5 3,321,325 5 /1967 Wisenbaker et aL106..;39 of the metal cations therein are potassium.

7. Size according to claim 1 wherein the monool is iso JULIUS FROMEPnmmy Examiner Propyl alcohoL T. MORRIS, Assz'slant Examiner.

8. Size according to claim 1 wherein the monool is 10 U.S CL X Rethanol.

